Chiral Chemistry (CC, Online ISSN 3106-8405) is an open-access quarterly journal dedicated to publication and dissemination of high-impact, original, and leading research in the field of chiral chemistry and technologies. The journal provides a platform for pioneering theoretical, experimental, and applied studies, promoting fundamental understanding, advancements, and applied innovations across a broad range of scientific and industrial applications.
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Chiral Chemistry (CC, Online ISSN 3106-8405) is an open-access quarterly journal dedicated to publication and dissemination of high-impact, original, and leading research in the field of chiral chemistry and technologies. The journal provides a platform for pioneering theoretical, experimental, and applied studies, promoting fundamental understanding, advancements, and applied innovations across a broad range of scientific and industrial applications.
more >
Chiral ligands play a crucial role in enantioselective transition-metal catalysis, not only by coordinating to metal centers and modulating their electronic properties, but also by providing the essential chiral environment for efficient enantiodiscrimination. ...
Chiral ligands play a crucial role in enantioselective transition-metal catalysis, not only by coordinating to metal centers and modulating their electronic properties, but also by providing the essential chiral environment for efficient enantiodiscrimination. For a given reaction, high enantioselectivities can often be achieved with different chiral ligands, offering valuable enantioinduction models, even when these ligands possess distinct structures and chiral environments. Herein, we report that a class of conformationally flexible C1-symmetric axially chiral phenanthroline ligands enables the formation of chiral copper catalysts capable of promoting the highly enantioselective ring-opening acyloxylation of cyclic biaryliodonium salts. Using this approach, a range of valuable axially chiral biaryl compounds bearing an ester group and a carbon–iodine bond were synthesized in good to excellent yield (up to 99%), with good to excellent enantioselectivity (up to 99.5:0.5 er).
L-amino acids are ubiquitous in biology, yet the origin of their homochirality is an enduring mystery. Prebiotic chiral selection process of amino acids could significantly influence subsequent molecular evolution and the emergence of life. However, the ...
L-amino acids are ubiquitous in biology, yet the origin of their homochirality is an enduring mystery. Prebiotic chiral selection process of amino acids could significantly influence subsequent molecular evolution and the emergence of life. However, the distribution of chirality of amino acids remains convoluted, which poses obstacles to the in-depth study of prebiotic chiral selection of amino acids. Here, we propose that minerals in the prebiotic environment might have hindered the absolute selection of L-amino acids to induce a random distribution of L- and D-amino acids during the early stages of life’s evolution. Pyrite, abundant in the prebiotic world, predominantly selected D-amino acids in the photocatalytic reductive amination of α-keto acids, resisting the enantioselectivity of chiral driving forces like chiral structures, magnetic fields, circularly polarized light, and chiral molecules. This resistance is due to the wavy atomic arrangement of pyrite surfaces, which causes larger reaction energy differences between enantiomers. Our findings provide evidence to assess the validity of prebiotic chiral selection scenarios for biomolecules, an important step in understanding the origin of life.
Owing to its intrinsic chirality, programmability and structural diversity, DNA functions as an effective chiral ligand for asymmetric catalysis in water. DNA hybrid catalysts are constructed by anchoring metal species into DNA scaffolds through covalent ...
Owing to its intrinsic chirality, programmability and structural diversity, DNA functions as an effective chiral ligand for asymmetric catalysis in water. DNA hybrid catalysts are constructed by anchoring metal species into DNA scaffolds through covalent or noncovalent strategies. These DNA-based catalytic systems exhibit potent reactivity and high enantioselectivity in various C–C, C–N, C–O, and C–F bond formation reactions in aqueous media. Importantly, their catalytic activity and product stereochemistry can be precisely directed by modulating DNA sequences, tertiary structures, metal species, and host-guest interaction. This review highlights recent advances in DNA-mediated asymmetric catalysis and discusses future prospects toward tailored stereocontrol under aqueous conditions.
Axially chiral binaphthyl scaffolds provide a robust platform for encoding permanent stereochemistry into conjugated polymer backbones while promoting nonplanar organization and higher-order aggregation. Building on our group’s earlier development ...
Axially chiral binaphthyl scaffolds provide a robust platform for encoding permanent stereochemistry into conjugated polymer backbones while promoting nonplanar organization and higher-order aggregation. Building on our group’s earlier development of multilayer 3D folding polymers and related achiral/chiral multilayer polymer series, we designed and synthesized the first enantiopure chiral multilayer polymers from enantiopure binaphthyl-derived monomers via CuI-assisted, Pd-catalyzed Sonogashira polycondensation. To probe structure–property relationships, the monomer library was designed to contrast flexible alkoxy-substituted systems with a conformationally constrained tethered analogue. The resulting polymers were obtained in moderate yields, with number-average molecular weights on the order of 103-104 g mol-1 and relatively narrow dispersities. UV–visible spectra showed the expected aromatic π-π* absorptions. Photoluminescence measurements in tetrahydrofuran (THF)/H2O mixtures displayed a nonmonotonic solvent-composition dependence, with emission enhancement at intermediate water fractions followed by quenching in more water-rich mixtures. Dynamic light scattering indicated the presence of light-scattering dispersed aggregates in CHCl3 under the tested conditions, while scanning electron microscopy revealed hierarchical agglomerates in the dried state, in which submicrometer particulates coalesced into micrometer-scale clusters. Together, these results show that axial stereochemistry and aggregation/packing behavior cooperatively influence radiative and nonradiative decay pathways in chiral multilayer backbones, providing useful design guidance for aggregation-responsive emissive polymer materials.
We report the first Ir(I)-catalyzed enantioselective intramolecular C–H silylation of ferrocenes for the efficient construction of planar-chiral 5- and 6-membered ferrocenyl silacycles. This method overcomes key limitations of existing Rh(I)-based ...
We report the first Ir(I)-catalyzed enantioselective intramolecular C–H silylation of ferrocenes for the efficient construction of planar-chiral 5- and 6-membered ferrocenyl silacycles. This method overcomes key limitations of existing Rh(I)-based systems, offering superior reactivity, enhanced cost-effectiveness, and broader substrate scope, including challenging C3- and C6-substituted derivatives, as well as excellent enantiocontrol under mild conditions without requiring exogenous H2 acceptors. The utility of the obtained planar-chiral scaffolds is preliminarily demonstrated through the synthesis of novel monophosphine ligands, which exhibit promising activity in asymmetric catalysis.
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product ...
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product synthesis. Denitrogenation demonstrates high activity and can engage in cyclization reactions with olefins, alkynes, carbon-heterocycles, aldehydes, and other reagents. This one-step operation enables the rapid construction of chiral heterocycles such as pyrroles and indoles, significantly shortening complex synthetic pathways. Innovations in chiral ligands, optimization of catalytic systems, and detailed studies on mechanisms have significantly enhanced the enantioselectivity and substrate applicability of denitrogenation reactions. This review highlights recent advancements in the synthesis of chiral heterocycles via denitrogenation reactions and systematically examines the reaction characteristics of various metal catalytic systems.
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated ...
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated in Rh-catalyzed asymmetric sulfonyl retentive S,N-difunctionalization of alkynyl N-sulfonylhydrazones with sulfenamides. The sulfonyl group or the corresponding sulfinic acid is retained in a formal migration. This mild and efficient protocol allows for straightforward construction of enantioenriched sulfonyl-based allylic sulfenamides with excellent chemo-, E/Z-, and enantioselectivity, thereby offering a creative strategy for achieving more atom-economic transformations of carbene precursors. Mechanistic studies reveal a three-step process involving S-allenylation, hydrosulfonylation, and an aza-Mislow-Evans rearrangement, with the hydrosulfonylation step governing enantioselectivity.
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction ...
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction of the related optically active organosilanes, organosulfides, organophosphine, and organochlorides. These compounds have shown considerable potential for preparing functional molecules and synthesizing natural products. Over the past few decades, considerable research efforts have focused on the design and development of transition-metal catalysts featuring chiral ligands for the asymmetric hydrogenation of such substrates. In parallel, in-depth mechanistic studies have been conducted to elucidate the pathways of these enantioselective hydrogenation reactions, significantly advancing the understanding of their catalytic behavior and stereocontrol. This review focuses on the recent momentum and key advancements in the enantioselective hydrogenation of vinyl silanes, vinyl sulfides, and vinyl chlorides. In addition, given the widespread industrial interest in these compounds, the practical utility of this transformation in the synthesis of chiral silanes, chiral thioethers, chiral alkyl chlorides, as well as related derivatives, is also discussed.
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic ...
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic atropoenantioselective amidation between axially prochiral biaryl dialdehydes and amides that efficiently affords axially chiral imides. This method operates under metal-free and mild conditions, exhibits broad functional group tolerance and substrate scope, and delivers products with excellent enantioselectivities. Furthermore, a wide variety of axially chiral imides, amides, and related derivatives can be accessed through enantio-retentive transformations, offering a versatile and attractive strategy for their synthesis.
Transition metal-catalyzed asymmetric C–H activation is vital for chiral molecule synthesis but faces challenges in remote C–H functionalization due to traditional metallacycle constraints and difficulties in long-range chiral recognition. This review ...
Transition metal-catalyzed asymmetric C–H activation is vital for chiral molecule synthesis but faces challenges in remote C–H functionalization due to traditional metallacycle constraints and difficulties in long-range chiral recognition. This review summarizes three core strategies to address these issues: template-assisted chiral ligand control, norbornene-mediated palladium catalysis, and bifunctional catalyst control. These strategies achieve high enantioselectivity for diverse chiral architectures. Future directions include expanding to para-C–H bonds of arenes and aliphatic C–H bonds, developing robust chiral mediators/ligands, and applying the methodology to natural products and complex materials.
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction ...
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction of the related optically active organosilanes, organosulfides, organophosphine, and organochlorides. These compounds have shown considerable potential for preparing functional molecules and synthesizing natural products. Over the past few decades, considerable research efforts have focused on the design and development of transition-metal catalysts featuring chiral ligands for the asymmetric hydrogenation of such substrates. In parallel, in-depth mechanistic studies have been conducted to elucidate the pathways of these enantioselective hydrogenation reactions, significantly advancing the understanding of their catalytic behavior and stereocontrol. This review focuses on the recent momentum and key advancements in the enantioselective hydrogenation of vinyl silanes, vinyl sulfides, and vinyl chlorides. In addition, given the widespread industrial interest in these compounds, the practical utility of this transformation in the synthesis of chiral silanes, chiral thioethers, chiral alkyl chlorides, as well as related derivatives, is also discussed.
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated ...
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated in Rh-catalyzed asymmetric sulfonyl retentive S,N-difunctionalization of alkynyl N-sulfonylhydrazones with sulfenamides. The sulfonyl group or the corresponding sulfinic acid is retained in a formal migration. This mild and efficient protocol allows for straightforward construction of enantioenriched sulfonyl-based allylic sulfenamides with excellent chemo-, E/Z-, and enantioselectivity, thereby offering a creative strategy for achieving more atom-economic transformations of carbene precursors. Mechanistic studies reveal a three-step process involving S-allenylation, hydrosulfonylation, and an aza-Mislow-Evans rearrangement, with the hydrosulfonylation step governing enantioselectivity.
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product ...
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product synthesis. Denitrogenation demonstrates high activity and can engage in cyclization reactions with olefins, alkynes, carbon-heterocycles, aldehydes, and other reagents. This one-step operation enables the rapid construction of chiral heterocycles such as pyrroles and indoles, significantly shortening complex synthetic pathways. Innovations in chiral ligands, optimization of catalytic systems, and detailed studies on mechanisms have significantly enhanced the enantioselectivity and substrate applicability of denitrogenation reactions. This review highlights recent advancements in the synthesis of chiral heterocycles via denitrogenation reactions and systematically examines the reaction characteristics of various metal catalytic systems.
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent ...
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent advances in the catalytic asymmetric synthesis of chiral organogermanes, highlighting a shift from traditional resolution methods toward asymmetric catalytic approaches. The content is organized into three main categories: (i) synthesis of C-stereogenic germanes, (ii) synthesis of Ge-stereogenic germanes, and (iii) synthesis of other chiral germanes, including planar, inherent, and axially chiral types. Key synthetic methodologies are systematically examined, such as enantioselective alkene hydrofunctionalization, carbene insertion, coupling reactions, and [2+2+2] cycloaddition, utilizing a variety of catalytic systems ranging from transition metals (Rh, Cu, Ni, Co) and Lewis acids to engineered metalloenzymes. Particular emphasis is placed on the mechanistic insights and ligand design principles that enable stereochemical control in these transformations. We hope this review will inspire chemists working in related areas and contribute to the future advancement of this field.
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic ...
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic atropoenantioselective amidation between axially prochiral biaryl dialdehydes and amides that efficiently affords axially chiral imides. This method operates under metal-free and mild conditions, exhibits broad functional group tolerance and substrate scope, and delivers products with excellent enantioselectivities. Furthermore, a wide variety of axially chiral imides, amides, and related derivatives can be accessed through enantio-retentive transformations, offering a versatile and attractive strategy for their synthesis.
